It is well known that the higher the viscosity of a liquid composition, the greater will be its residence time when applied to a non-horizontal surface such as a wall. This viscosity can be increased in many ways. Especially for compositions containing a hypochlorite bleach, a variety of formulations have been proposed, but thickening systems have also been proposed for aqueous cleaning compositions of a pH not higher than 7.0 . GB No. 1,240,469, for instance, discloses compositions, suitable for cleaning metal, glass and painted surfaces, which compositions have a pH not higher than 7.0 and comprise (a) an inorganic acid, an organic acid or an acidic salt (b) a cationic detergent and (c) a water insoluble or partially water soluble covalent compound other than the compounds under (b) and which contains oxygen or halogen and at least one hydrocarbon chain of at least four carbon atoms.
As component (c) can more particularly be used an ester of an inorganic acid, a fatty acid or an ester of a fatty acid, a carboxylic acid ester in which the hydrocarbon chain derived from the alcohol has at least four carbon atoms, an alkyl chloride, a hydroxyl compound or substituted hydroxy compound, and the hydroxy compound is preferably water insoluble, such as a fatty alcohol, containing from 4-30 carbon atoms in at least one alkyl chain.
As cationic detergent only an amine oxide of a special structure is mentioned, which is exemplified by a large number of representatives, the actual application of quaternary ammonium salts being neither disclosed in general terms, nor in specifically exemplified representatives.
U.S. patent specification No. 3,997,453 discloses a stable, cold water dispersible fabric softening composition comprising from about 60 to 20% by weight of a cationic quaternary ammonium softener, an organic anionic sulfonate, the weight ratio of the cationic softener to the anionic detergent being from about 40:1 to 5:1 and wherein the anionic sulphonate being selected from amongst benzene or naphthalene sulphonate or a polyalkyl substituted aromatic sulphonate with one of the alkyl groups having not more than 18 C-atoms and each of the remaining alkyl group having not more than 2 carbon atoms.
Considering the statements in U.S. patent specification No. 3,997,453, lines 42-45 and lines 57-64 of column 1, it is clear that a person skilled in the art would only be led away from trying to use combinations of cationic quarternary compounds and an anionic sulphonate as thickening composition. A person skilled in the art was even fortified in that prejudice on account of Kunishov et al, Tr. Mezhdunar. Kongr. Paverkhn.--Akt. Veshchestvam, 7 th 1976 (publ. 1978), 3, 150-8, Nats. Komm. SSSR Poverchn.--Akt. Veschchestvam Moscow, USSR.
From e.g. Journal of Colloid and Interface Science, vol. 57, no. 3, December 1976, 575-577; Journal of Physical Chemistry, vol. 83, no. 17, 1979, 2232-2236; Ber. Bunsenges. Phys. Chem. 85, 255-276 (1981) and ibidem 86, 37-42 (1982) a great interest appears for research relating to viscoelastic surfactant solutions, containing a quaternary ammonium compound derived from salicylic acid, m-chlorobenzoic acid and p-chlorobenzoic acid, while moreover from Journal of Colloid and Interface Science, vol. 57, no. 3, December 1976, page 576 and from Wan. L.S.C., J. Pharm. Sci. 55, 1395 (1966) it could anyhow be derived by a skilled person that the desired increase in viscosity could not generally be obtained in the pH range of from 1.6 to 2.5, depending on the organic acid to be applied with, e.g., cetyl trimethyl ammonium bromide.
Moreover, the continued exceptional interest taken in the last few years in the rheological properties of aqueous compositions, containing quaternary ammonium ions and salicyclic acid and some sulphonates of alkyls, clearly appears from, e.g., Seifen-Ole-Fette-Wachse-111 Jg. No. 15/1985, 467-471 and 200-202 and Journal of Colloid and Interface Science, Vol. 106, No. 1, July 1985, 222-225, whereas from the European patent applications Nos. 144,166 and 137,871 it appears that people skilled in the art, when looking for alternative improved thickening systems, also began to consider the application of tertiary amine oxides in certain specific compositions.
It will be appreciated from these two patent applications, that the former prejudice that cumene sulphonates, xylenes sulphonates or toluene sulphonates and the like were far from attractive for use in thickening compositions of aqueous solutions, continued to exist.
More particularly, from lines 5-8 of page 3 and lines 4-25 and more particularly lines 11 and 12 of page 5 of EP 137,871, it appears that skilled people were primarily looking for other combinations of specific amine oxides and anionic surfactants which are substantially different from cumene sulphonate, xylene sulphonate, toluene sulphonate and which have a more complex structure and are therefore more difficult to handle. Moreover, such compounds are higher in price.
As result of extensive research and experimentation it has suprisingly been found now that improved thickened aqueous single phase compositions could be obtained, which comprise:
(a) from 0.1% to 10% by weight of a surfactant selected from the group consisting of (1) quaternary ammonium compounds, wherein at least one of the hydrocarbon groups linked to nitrogen is a linear or branched alkyl group containing at least 12 carbon atoms and preferably 16-20 carbon atoms, and being saturated or unsaturated, and wherein two or three of the groups linked to the nitrogen are independently unsubstituted or substituted alkyl groups which contain 1 to 6 carbon atoms, and wherein one or more of said alkyl groups may contain an aryl substituent or may be replaced with an aryl group, and wherein an anion may be present such as halide, acetate, methosulphate, and the like, and (2) tertiary amine oxides wherein at least one of the hydrocarbon groups linked to nitrogen is a linear or a branched alkyl group containing at least 16 carbon atoms and preferably 16-20 carbon atoms being saturated or unsaturated and wherein two of the groups linked to the nitrogen are independently unsubstituted or substituted alkyl groups which contain 1-6 carbon atoms and wherein one or more said alkyl groups may contain an aryl substituent or may be replaced by an aryl group, PA1 (b) from 0.01% to 10% by weight of an organic, anionic sulphonate selected from the group consisting of cumene sulphonate, xylene sulphonate, and toluene sulphonate, in their acid or salt form, and mixtures there of, and PA1 (c) from 0.5 to 15% by weight of an acid PA1 (d) from 0.1 to 30% by weight of hydrogen peroxide PA1 (e) water, wherein one or more cleaning, disinfecting and/or odorizing agents may be dissolved or dispersed, the percentages by weight being calculated on the weight of the total aqueous composition, and the pH of said composition being from 0 to 6.
Examples of such cleaning, disinfecting and/or odorizing agents are auxiliary detergents, acids, detergent builder salts, perfumes or antibiotics.
A preferred embodiment of the present invention is formed by thickened aqueous cleaning compositions having a pH of not more than 7 and preferably between 0 and 6 and more preferably between 0-4, and containing 1-15% by weight of an acid, normally occurring in cleaning compositions.
Typical examples of quaternary ammonium compounds referred to under (a) are:
ethyl-dimethyl-stearyl ammonium chloride, PA0 ethyl-dimethyl-stearyl ammonium bromide PA0 cocoalkyl-trimethyl ammonium chloride, PA0 hydrogenated tallow-trimethyl ammonium chloride, PA0 hydrogenated tallow-trimethyl ammonium bromide PA0 stearyl-trimethyl ammonium chloride, PA0 stearyl-trimethyl ammonium bromide, PA0 cetyl-trimethyl ammonium bromide, PA0 lauryl-dimethyl-ethyl ammonium chloride, PA0 tallow trimethyl ammonium chloride, PA0 tallow trimethyl ammonium bromide, PA0 myristyl-propyl dimethyl ammonium chloride and the corresponding methosulphates, acetates, and the like. PA0 (hydrogenated) tallow-trimethyl ammonium chloride, PA0 (hydrogenated) tallow-trimethyl ammonium bromide, and PA0 cetyl-trimethyl ammonium chloride. PA0 bis(2-hydroxy ethyl) cetylamine oxide, PA0 bis(2-hydroxy ethyl) tallowamine oxide, PA0 bis(2-hydroxy ethyl) hydrogenated tallow amine oxide, PA0 bis(2-hydroxy ethyl) stearylamine oxide, PA0 bis(2-hydroxy propyl) tallowamine oxide, PA0 bis(2-hydroxy propyl) stearyl amine oxide, PA0 dimethyl tallowamine oxide, PA0 dimethyl cetylamine oxide, PA0 dimethyl stearylamine oxide, and PA0 di-ethyl stearylamine oxide. PA0 cetyl-dimethyl amine oxide.
Preferred cationic ammonium compounds contain saturated alkyl groups in view of their stability towards the hydroperoxides:
Most preferably cetyl trimethyl ammonium chloride (hexadecyl trimethyl ammonium chloride) is used.
Typical examples of tertiary amine oxides referred to under (a) are:
A preferred amine oxide is:
The amine oxide and/or quaternary ammonium compound may preferably be used in amounts from 0.1% to 5% by weight based on the total weight of the composition dependent on the viscosity and the type of the agent desired.
A preferred embodiment of the present invention is formed by thickened compositions containing one or more salts of the specified sulphonates. Typical salts of the sulphonates specified under (b) are the sodium, potassium, ammonium, lower amine and alkanolamine salts, of which the sodium salts are preferred.
Typical acids which may be applied in the compositions of the present invention are sulphuric acid, phosphoric acid, sulphamic acid, citric acid, acetic acid, formic acid or an acidic salt of the type conventionally used in cleaning compositions, or combinations thereof in an amount of from 1-15%. More preferably, citric acid should be used in an amount from 1-10% by weight, based on the total composition. The compositions according to the present invention exhibit a viscosity of at least 200 mPa.s at 20.degree. C. and shear rate of 0.1 sec.sup.-1.
A preferred further additive is a water-soluble hydro peroxide, such as hydrogen peroxide or peracetic acid having disinfecting and bleaching activity, most preferably hydrogen peroxide. Such hydrogen peroxide-containing cleaning compositions avoid the risk of evolution of chlorine gas such as involved with traditional hypochlorite cleaning compositions when inadverbently contacted with acids.
For compositions exhibiting optimum thickening effects, the ratio of the weights of the quaternary ammonium compound or tertiary amine oxide to the sulphonate is in the range from 0.1-6 and preferably from 1.5-2.5 and more preferably around about 2.0.
A preferred embodiment of the invention is formed by the thickened cleaning composition which comprises:
______________________________________ (a) tallow trimethyl ammonium chloride 2.24% by weight (as 50% solution Arquad T50 .RTM.) (b) sodium xylenesulphonate (40%) 1.26% by weight (c) citric acid monohydrate 5% by weight (d) Perfume Floral Rose (IFF) 0.1% by weight (e) water 91.4% by weight ______________________________________
which showed the following viscosity values at different shear rates, using a Haak Rotovisco RV 100 viscosimeter.
______________________________________ shear rate sec.sup.-1 viscosity m Pa.s. at 20.degree. C. ______________________________________ 0.1 300 0.3 200 3 130 30 87 300 18 ______________________________________
The thickening systems described above display a viscosity temperature relationship that has a parabolic profile with the maximum viscosity being exhibited at a temperature in the range from 0.degree. C. to 30.degree. C. An increase in chain length of higher alkyl chain in the quaternary ammonium ion or amine oxide in general increases the temperature at which this peak occurs while a reduction in this higher alkyl chain length and/or branching in this alkyl group, reduces the temperature at which the maximum viscosity is produced by the system.
It will be appreciated by persons skilled in the art that the ideal situation, wherein the viscosity of the composition should be independent of temperature over a temperature range which encompasses the practical domestic conditions, i.e., from 5.degree.-25.degree. C., is approached most closely by the compositions of the present invention, employing a blend of surfactants and specific sulphonate(s), the application of which would certainly be rejected by persons skilled in the art.
It will be appreciated by persons skilled in the art that the optimal characteristics of the compositions of the present invention will be governed by the specific kind of surfactant (quaternary ammonium ion or amine oxide), kind of sulphonate, kind of acid in the composition, amount of acid electrolyte concentration in total composition, ratio of weights of the surfactant-sulphonate combinations, and counter ion of the sulphonates. The thickening compositions according to the present invention have however appeared to be rather insensitive to other types of ingredients occurring in the complete aqueous cleaning composition, such as perfume.
For example, for optimal results, the weight ratio of tallow trimethyl ammonium chloride and sodium xylene sulphonate in citric acid solution of 4.5% by weight (100%), i.e., 5% of hydrated citric acid, may vary from 2.0-2.5, and more preferably 2.15-2.25, while acceptable compositions for practical purposes may show ratios from 0.5-4.0 (based on 100% ingredients).
It will be appreciated that another feature of the invention is formed by a thickening premix composition which comprises at least:
(a) a surfactant selected from the group consisting of quaternary ammonium compounds and tertiary amine oxides as defined hereinbefore, and
(b) an organic, anionic sulphonate selected from the group consisting of cumene sulphonate, xylene sulphonate, and toluene sulphonate, in their acid or salt form, and mixtures thereof, in a weight ratio of both ingredients as indicated before.
The application of such thickening premix compositions has appeared to be rather insensitive to the presence of other ingredients in the final cleaning composition, e.g., perfume. Such thickening premix compositions have been found to consist of homogeneous mixtures of components (a) and (b) and to exhibit a long storage stability. When mixed with water or an aqueous solution they display a surprising thickening effect.
Another feature of the present invention is formed by the application of the thickened aqueous single phase compositions according to the usual methods of this specific art of cleaning non-horizontal surfaces such as walls, windows and sanitary fittings.